Black dye.



PAUL JULIUS, OF LUDlVIGSI-IAFEN, GERMANY, ASSIGNOR TO THE BADISOHEANILIN AND SODA FABRIK, OF SAME PLACE.

BLACK DYE.

SPECIFICATION forming part of Letters Patent No. 644,237, dated February27, 1900.

Application filed September 10, 1898. Serial No. 690,650. (Specimens) Toall whom it nut/y concern:

Be it known that I, PAUL JULIUS, doctor of philosophy, a subject of theEmperor of Ans tria-Hungary, residing at Ludwigshafen-onthe-Rhine, inthe Kingdom of Bavaria and Empire of Germany, haveinvented new anduseful Improvements in the Manufacture of New Disazo Dye, of which thefollowing is a specification.

I have invented a group of secondary disazo dyes from a certainnitro'amido-phenolsulfo-acid: a so-called middle component namely,alphanaphthylamin or the alphanaphthylamin sulfo-acid known as Oleves,which is a mixture of 1.6 and 1.7 sulfo-acid and a further componentnamely,beta-naphtho], alpha-naphthylamin or naphthol-sulfoacid,(1.4 or 1.5,) ethyl-beta-naphthylamin, 1.8-naphthylamin sulfo-ac'id,beta-naphthoL disulfo-acid R, and 1.3.G-alpha-naphthol-disulfo-acid. Inan application of even date herewith I claim this group ofcoloring-matters generically and also the specific coloringmatters fromnaphthol-sulfo-acid, (1.4 or 1.5.) In the present application I do notclaim these, but desire to protect by Letters Patent the specificcoloring-matter having beta-naphthol as end component andalpha-naphthylamin as middle component.

The nitro-amido-phenol-sulfo-acid which I use in this invention has beendescribed in the specification of German Letters Patent No. 93,443, andthe constitution sulfo-acid hereinbefore defined in about five hundred(500) parts of water and diazotize by treatment with about fifteen (15)parts of hydrochloric acid (containing about thirty (30) per cent. H01)and about seven (7) parts of sodium nitrite at the ordinary temperature.Pour the diazo solution into a solution of about fifteen (15) parts ofalpha-naphthylamin in six hundred (600) parts of water and fifteen (15)parts of hydrochoric acid, (containing about thirty (30) per cent. H01.)Stir at a temperature of about from thirty-five (35) to seventy-fivedegrees centigrade till a test portion on filter-paper gives no reactionof diazo compound. This usually requires from ten to twenty-four hours,the time depending principally upon the temperature maintained. Filterthe intermediate coloringmatter obtained and wash with cold Water.Dissolve the intermediate coloring-matter in about two thousand fivehundred (2,500) parts of boiling water, to which about seventeen (17)parts of caustic-soda lye (containing about thirty-five per cent. NaOH)are added. Allow the solution to cool and add seven and a half (7%)parts of sodium nitrite in the form of a concentrated solution. Pourthis mixture into a dilute sulfuric acid containing about two hundred(200) parts of ice, thirty (30) parts of sulfuric acid, (containingabout ninety-five (95) per cent. H and ninety parts of water. Stir whilemixing, and subsequently a precipitate separates out which is at firstdark in color and gradually becomes brown. Filter, stir with cold Water,

and pour into a solution of about fifteen (15) parts of beta-naphthol,which is rendered alkaline, with a slight excess of caustic soda. Theformation of coloring-matter is soon completed. Add common salt tocomplete the precipitation of the coloring-matter and filter and press.Purify, if necessary, by redissolving and reprecipitating. If desired,the combination can be effected without first collecting the diazocompound by filtration.

My new coloring-matter dyes Wool in dark bluish shades, which turn deepblack by subsequent treatment with chromates, and is characterized byits behavior on reduction with ammonium sulfid in ammoniacal solution.When suitably reduced, a step-by-step reduction can be observed and anamido body can be obtained which can be diazotized and combined withR-salt, yielding an azo dye which is violet blue in the presence ofalkalies, turning to intense red on treatment with hydrochloric acid,just like the R-salt azo dye of ortho nitro ortho amido-para-sulfo-acid. This test can be effected as follows: Heat up one (1) gram ofcoloring-matter with one hundred (100) cubic centimeters of water andadd fifteen cubic centimeters of ammonia, (containing twenty per cent.NI-I The solution is deep dark blue in color. Add drop by drop to thenearly-boiling solution some fresh ammonium sulfid. The liquid turnsthrough violet to deep red. This marks the first step of the reduction.Add more ammonium sulfid drop by drop, avoiding any considerable excess,and continue the treatment. The liquid turns brown. This marks anotherstage of the reduction, and the liquid contains thenitro-amido-phenol-sulfo-acid reproduced. 0001 the liquid, add excess ofhydrochloric acid, diazotize With sodium nitrite, filter and run thediazo-solution into an alkaline solution of R-salt containing, say, two(2) grams R-salt and twelve (12) grams soda in one hundred and twenty(120) parts water. A violet-blue azo dye is obtained which turns to redin the presence of hydrochloric acid.

My new dye with beta-naphthol as end component is further characterizedby yielding a violet-black solution in concentrated sulfuric acid.

The coloring-matter yields a blue solution when dissolved in onethousand times its weight of water. On adding caustic soda to thissolution scarcely any perceptible change of color takes place when thesolution be looked at in bulk. Hydrochloric acid on addition to thesolution produces a violet-red precipitate, and ferric chlorid onaddition to the solution produces also a violet-red precipitate.

Now what I claim is-- As a new article of manufacture the specific newcoloring-matter which can be derived from ortho nitro ortho-amidophenol-sulfoacid, alpha-naphthylamin and beta-naphthol and which ischaracterized by its behavior on suitable reduction with ammonium sulfidin ammoniacal solution in that a step-by-step reduction reproducing thenitro-amido-phenolsulfo-acid can be observed and which yields a violetblack solution in concentrated sulfuric acid, a blue solution whendissolved in water, scarcely any perceptible change of color in bulk onadding caustic soda, a violet-red precipitate with hydrochloric acid andalso a violet-red precipitate with ferric chlorid, all substantially asdescribed.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

PAUL JULIUS.

Witnesses:

BERNHARD C. I-Inssn, ADOLPI-I REUsTINenR.

